Organic compound



Patented Sept. 2, 1941 ORGANIC COMPOUND John Stanley Herbert Davies, Blackley,'Manchester, England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application July 26, 1939, Serial No. 286,584. In Great Britain August 2, 1938 11 Claims.

This invention relates to new organic compounds, and to a process for their manufacture. More particularly, this invention deals with the preparation of novel p-isoindigo derivatives, which may be represented generically by the formula RO=CR l l I A=C-NH HNG=A In this formula, R, R are aromatic radicals of the benzene or naphthalene series to which the 10 carry Simple 'substituentsg S as chloro C, C atoms of the heterocyclic rings are attached or m mtro or m groups- A slmhar in adjacent positions, while A, A represent the senes of compotndsgobtamed by an ajmalogolm radicals of compounds which are wholly or partly process is descrlbed m copendmg apphcatlon of cyclic d which include t atomic grouping Hanford, Serlal NO. 2I?0,14=6, filed September 15th, CH2 CO in t cyclic Structure 15 1933, and issued April 23 1940, its U. S. Patent when R is phenylene, a Subgroup of No. 2,198,166. From their reactions, these new pounds results having the general formula compounds appear to be tautomenc, the tauto' mer1c forms being represented by the two gen- 0 O eral formulae I and II below. 7

2O o=c- Z A=C-1LH Hl IO=A 2) I wherein A, A has the same significance as above. This subgroup may be designated generically as 1, 3.3 E 1-derivatives of 3, 3-bis-isoindolenylidene, the 0 name being derived from the simple, compound indole by the following hypothetical metamorphosis: g

II s CH CH3 CH1 ("1' 1 Z Z H 0 N=CH HG=N o Indole Pseudo-indole Isoindolenine g or Indolenine NH a: (a) g 1 1 H2O NH wherein R, R stand for phenylene or naphthylene 3 3 bi -is0i d0]eny1idene radicals, which may carry simple substituents', It is an object of this invention to provide such as chlolfo atoms or methyl, nitro amino new organic compounds having, variously, utility ups, bllt'ln which the two C atoms of the as intermediates for the synthesis of dyestuffs, heterocyclic ring are attached in acent posias pigments, and in the arts f dyeing textiles tions. For distinction, form I will hereinafter and of making lakes. It is a further object of be referred s pt wh le form this invention to provide processes for obtaining W111 be referred LIV-(11171110118 de Vasuch compounds. Other and further important tlVeS- objects of this invention will appear as th d We have now found that valuable new coloured scription proceeds. omp unds may beobtained by treating the com- The manner in whi ch We accomplish the afore- P01111018 0f the above mentioned copending pp going objects will now be apparent from the ions, or their monoor di-alkyl or -aralkyl following description.

others, with organic compounds which are cyclic grouping HN-C=S HzC- Hl C=C where M stands for hydrogen or alkyl.

The condensation is conveniently eifected by heating the reactants together, preferably in a suitable liquid such'as'dimethylaniline or technical monochloronaphthalene. In most cases condensation takes place quickly and easily and good yields of the condensation products are obtained.

We have also found that such of the new condensation products, as are obtained from those starting materials containing -CH2.CO- grouping which also contain aryl radicals or other nuclei which can be sulphonated, can be con verted to further new compounds, which are water soluble by sulphonation.

Sulphonation can be conveniently effected by treating with a sulphonating acid, e. g., concentrated sulphuric acid, .or oleum, if necessary, at a raised temperature.

The compounds which are obtained by the process of this invention are mostly highly coloured. The insoluble ones can be used as vat dyestuffs or as pigment ones. The soluble ones can be used as bases for lakes and as dyestuffs for W001 and cotton. Both the soluble and the insoluble ones can also be used as dyestufi intermediates.

The following examples, in which parts are by A mixture of 5.8 parts of oc-IIELPhthOl, 3.2 parts of 1:l-di -(methylmercapto) 3:3-bis-isoindolenylidine (made by treating the product of Example 1 of copending application Serial No. 272,056, above referred to, with dimethyl sulphate and alkali, i."e., methylating both mercapto substituents) and 22.5 parts of dimethylaniline is boiled for minutes, allowed to cool and filtered. The filter-paste is washed with ethyl alcohol and dried.

The dry product, which is fast to light, dissolves in concentrated sulphuric acid with a blue colour. It dissolves in aqueous alkaline hydrosulphite solution with a bluish-red colour and the solution dyes cotton in greenish-blue shades. It does not melt below 300 C. The product corresponds in structure to Formula 2 above, wherein A represents the radical The same compound may be made from 1:1- di-(ethylmercapto) bis-isoindolenylidine instead of from the dimethyl compound. The diethyl compound itself is made in a similar way to the dimethyl.

Example 2 5 parts of 1,1-dimercapto-3,3-bis-isoindolenylidene (prepared by passing hydrogen sulfide into a cooled alcoholic solution of phthalonitrile and ammonia; see Example 1 of British Patent No. 516,342) are heated with 25 parts of alphanaphthol at 210 to 220 C. for about two hours and until evolution of hydrogen sulphide is practically complete. The mixture is cooled, the excess of alpha-naphthol is removed by means of ethyl alcohol and the residue is crystallised from chloronaphthalene. The product appears to be the same as that of Example 1.

Example 3 5 parts of the product of Example 1 are gradually stirred into 50 parts of 2% oleum at about 10-15 C. and stirring continued for about one hour at the same temperature. The solution is poured into 250 parts of ice-water, the mixture filtered, the filter-cake washed acid-free with 2% aqueous sodium cholride solution and dried.

The dry product, which appears to be a sulphonic acid of the compound formulated in Example 1, dissolves in water with a greenish-blue colour, and dyes wool in greenish-blue shades of very good fastness to light.

Example 4 4.32 parts of tetrachloro-l:1-dimercapto-3:3- bis-isoindolenylidene (as made in copending application Serial No. 272,056) 4.32 arts of alphanaphthol and 30 parts of (technical) monochloronaphthalene are heated together at 250-270 C. for 1 hours. Hydrogen sulphide is evolved and on cooling a deep bluish-green coloured solid separates. The mixture is diluted with 5-10 parts of benzene or light petroleum to facilitate filtration, and the solid filtered- 01f, Washed with benzene or petroleum and dried.

The dry product is similar to that of Example 2. It dissolves in concentrated sulphuric acid with a bluish-green colour and in pyridine with a deep green colour. It dyes cotton in green shades from a reddish-alkaline hydrosulphite vat.

Example 5 HzN- NH2 A=C-NH HNC=A wherein A designates the radical Example 6 with Warm dilute sodium hydroxide solution to remove unchange 2-hydroxy-3-naphthoic anilidev and dried.v

Thedry product is deep greenish-black in colour. It dissolves in concentrated sulphuric acid with a greenish-blue colour, in pyridinerwith a green colour, and in aqueous alkaline hydrosulphite with a redd-ishebrown colour. The latter solution dyes cotton in green shades.

. Condensation products ggg ggag Starting material I Li ht Shade on cotton Colour fastgness from alkaline Shade on wool hydrosulphite vat 1 4-chloro-1-naphthol Blue=grey Excellent.-. Green-blue Bluish-green. 2 -methoxy-1-naphthoL... Greonish-grey. do Greenish-grey Green. 3 5-methylarnino-a-naphth Greenish-black. 4 5-B-hydroxy-ethylarnino-l-naphth0l. rey Grey Grey. 5 lt5-dihydroxy-naphfhalene do Greenish-grey.-- Bluish-grecn. 6 1:8 dihydloxy-naphthalene do. Green Green. 7 Resorcino] Greyish-blue Bluish-grey. 8 Bz-hydroxy-l,Z-benzoearbazole Greyish-violet.-. dish ey Reddish-grey. 9 2:4-diketo-l: :4-tetrahydroquinoline Violet Excellent. B1uish-violet 10 1:3-diketo-l: z4-tetrahydro-isoquinoline Blue... Goodu- Blue ll 1:4-diketo-l:2z3z4-tetrahydro-isoquinoline Greyish-blue Excellent.-. Bluish-grecnun In all the above cases, the product has the general Formula 2 above, wherein A is in each case the bivalent radical of the corresponding starting compound named in the first column of the above table.

Thus, in item 4, A representsthe radical HN-CzH4OH in item 8, the radical Example 7 p A mixture of 7.9 parts of 2-hydroxy-3 -naphthoic anilide, 3.2 parts of .1:1-di-(methylmercapto) 3:3-bis-isoindolenylidene and parts of technical monochloronapthalene is heated at 260-280 C. for 1%, hours. Th mixture is cooled, diluted with 5-10parts of benzene or light petroleum and filtered. 'I'hefilter -paste is extracted Example 8 A mixture of 7.8 parts of G-ethoxythioindoxyl, 3.2 parts of l:1'-di-(methylmercapto) 3:3-b'isisoindolenylid'e ne and 22.5 parts of dimethylaniline is boiled for a quarter of an hour, cooled and filtered. The filter-paste is Washed with benzene, and dried. '7

The dry product is dark purple in colour. It dissolves in concentrated sulphuric acid with a blue colour and in aqueous alkaline hydrosulphite with a red colour. It is probably 1:1-di-(ethoxy- I thioindoxyliclene) 3 3'-bis-isoindolinylidene, corresponding to Formula 2 above, wherein A designates the radical Example 9 5 parts of product of Example 8 are stir-red into parts'of 100% sulphuric acid during a quarter of an-hourat10 15 C. Stirring'is continued for three quartersof an'hour longer and the mixture'is then poured into 250 parts of icewater and filtered." The filter-paste is washed acid free with 10% aqueous sodium chloride solution and dried. l

The dry product dissolves in 1 water with a greenish blue colour.

' "Example 10 V The 'coinpound'of Example 8 can also be made by heating 2.94'parts of'1;1-di-mercapto-3,3- bis-isoindolenylidene (see Example 2 above) and 5.82 parts of fi-ethoxythioindoxyl in 30 parts of technical monochloronaphthalene at 250-270 C. for 8 hours. Hydrogen sulphide is evolved and on cooling the reaction mixture the product crystallises out. It is filtered, Washed With petrol or benzene and dried.

7 Example 11 48 parts of 2:1-naphthathioindoxyl, 19.3 parts of -1:1-di-(methylmercaptol 3:3 -b-is-isoindo1enylidene and 10!) parts of dimethylaniline are boiled with stirring for 1 hour, allowed to cool and filtered. The precipitate is washed with benzene and dried. Excess 'naphthathioindoxyl is removed by extracting with hot dimethylaniline.

The dry product is blue and dyes cotton in green shades from an olive-green alkaline hydrosulphite vat. The structure of the product corresponds to Formula 2 above, but A here designates the radical Example 12 Example 13 The following table shows the colour and light fastness of the compounds obtained from 1:1'-di- (methylmercapto) 3:3'-bis-isoindolenylidene and g other thioindoxyls as mentioned in the first column, and also the colour of the dyeings on wool of the compounds obtained by sulphonating the condensation products.

divided, its colour is purple. It has the constituwherein A has the same significance as above in this example.

(AnaZyses.Found C=75.3; H=4.8;

N=9.6; S=7.2% CzeHreONaS requires 0:741; H=4.5;

N=9.9; S=7.6%) Example 15 A mixture of 7 parts of 1-phenyl-3-methyl-5- pyrazolone, 3.2 parts of 1:1'-di-(methylmercapto) 3:3'-bis-isoindolenylidine and 22.5 parts of dimethylaniline is boiled for -15 minutes, and filtered. The filter-paste is extracted with benzene to remove excess of the phenylmethylpyrazclone.

The product forms small glistening crystals with a voilet sheen and does not melt below 300 C. t dissolves in concentrated sulphuric acid with a crimson colour and in aqueous alkaline hydrosulphite with a reddish-brown colour. It dyes cotton violet shades. It is believed to be di- (phenylmethyl pyrazolonylidene) 3:3'-bis-iso indolinyledene.

The structural formula therefore may be represented by Formula 2 above, wherein A desig- Gondcnsation product 533322 Thioindoxyl Li ht Shade on Wool Colour fastiess and cotton Thioindoxyl Greenish-grey. Excc1lent Bluish-green. 5-chloro-7-methyl-thioindoxyll Grey do Yellowish-green. 6-chloro+methy1-thioindoxyl Greyish-blue Very good. Greenish-blue. 1:2-naphtha-thioindoxyl Reddish-grey Excellent. Do. 2:3-naphtbe-thioindoxyl Green do Yellowish'green.

Example 14 nates the 4,4-bivalent radical of 1-phenyl-3- A mixture of 3.2 parts of 1:1'-di-(methylmerl =CNCH3 (AnaZyses.-Found C=78.7 H=5.0 N=10.4%

C34H24O2N4 requires C=78A7 H=4.62 N=10.76%)

The product s01uble in hot benzene separates on cooling as a dark crystalline precipitate with a brownish sheen. It is purified by crystallising from hot solvent naphtha. When it is finely methyl-5-pyrazolone, in other words the radical (Analyses-Found C=75.2 H=4.6 N=14.0 CseHzsOzNe requires 0:75.26 H=4.53 N=14.63%)

Instead of 1:1'-di-(methylmercapto) 3:3'-bisisoindolenylidene, the corresponding dipropyl compound may be used as a starting material. Also the dimercapto compound itself may be used.

Example 16 5 parts of the product of Example are stirred into parts of 2% oleum at 10-15 C. and stirring continued at this temperature for 10 hours, the temperature is then raised to C. and kept at this for 1 /2 hours. The solution is poured into 250 parts of ice-water and the precipitate obtained is filtered 011" and dried.

Example 17 9 parts of 1-(4'-nitro) phenyl-3-methyl-5pyrazolone, 6.4 parts of 1:1-di-.(metl1ylmercapto) 3:3-bis-isoindolenylidene and 50 parts of dimethylaniline are boiled together for about half an hour, allowed to cool and filtered. The precipitate is again boiled with dimethylaniline and filtered hot. After cooling, the precipitate is washed with petrol ether. When in a finely divided condition, it is bluish-black in shade. It dissolves in aqueous alkaline hydrosulphite with a yellow-brown colour, and a reddish-blue pre cipitate is formed when the solution is aerated.

Example 18 24 parts of rhodanine s---c s 19.3 parts of l:1-di(methylmercapto) 3:3'-bisisoindolenylidene and 100 parts of dimethylaniline are boiled together for /2- /.1 hour. The mixture is filtered hot and the precipitate, when cooled, is washed with ethyl alcohol. It is then again boiled with dimethylam'line and then with acetone to remove any impurity and excess rhodanine. After washing with alcohol, filtering and drying, a violet solid remains. The structure of the product corresponds to Formula 2 above, but A here designates the radical ll o t ts I claim: 1. A compound of the formula ri=ri A=c-Nn HNC=A wherein R. and R are aromatic radicals havin not more than carbon atoms in their cyclic configuration, the C, C atoms of the rings N-C above shown being attached to said aromatic radicals in adjacent positions, while A, A represent the radicals of compounds which contain at least one closed rin in their structure and which include one of the tautomeric groupings -CH2.CO-- and -cH=c(oH in the sa .i d closed ring,

\R R wherein R and R are aromatic radicals having not more than 10 carbon atoms in their cyclic configuration, the C, C atoms of the rings let above shown being attached to said aromatic radicals in adjacent positions, while the groups represent each, the radical of a heterocycllc component.

3. A compound of the formula wherein A represents the divalent radical of a pyrazolone compound.

4. A compound of the formulain the cyclic structure.

6. A process as claimed in claim 5, wherein the cyclic compound is a thioindoxyl.

7. A process as claimed in claim 5, wherein the cyclic compound is a pyrazolone.

8. A process as claimed in claim 5, wherein the cyclic compound is an alpha-naphthol.

9. A compound of the formula.

it it wherein A represents the divalent radical of a tautomerized alpha-naphthol.

10. A compound of the formula wherein A represents the divalent radical of a phenyl-methyl-pyrazolone.

11. A compound of the formula wherein A represents the divalent radical or a thioindoxyl.

JOHN STANLEY HERBERT DAVIES. 

